United States Patent Office
atented Sept. 28, 1964
1.
3,554,450
PROCESS FOR THE MANUEFACTURE OF
ACRYELONTRLE
onas Karact, New York, N.Y.; Edna Yadven. Kamiet,
executrix of said Josias Kanet, deceased, assignor, by
mesne assign eats, to Edia Y. Kaanet, doing business
as The Kainie Laboratories, New York, N.Y.
No Drawing. Fied Sept. 4, 1959, Ser. No. 839,570
4 Clains. (C. 260-465.9)
This invention relates to a process for the manufacture
of acrylonitrile. More particularly, this invention relates
to a process whereby acrylonitrile may be manufactured,
in good yields, from cheap and readily available industrial
intermediates-acetaldehyde and hydrogen cyanide.
Acrylonitrile has become an extremely important chem
ical article of commerce, widely used in the manufacture,
of synthetic rubbers, plastics, fibers, films, plasticizers, dye
stuffs, pharmaceuticals, solvents and other products.
A tremendous technology has developed and several 20
thousand patents have issued on the manufacture of acry
lonitrile by the dehydration of ethylene cyanohydrin
(from HCN and ethylene oxide) and by the reaction of
acetylene with HCN. Lactonitrile (which is isomeric with
ethylene cyanohydrin) made by the reaction of acetalde
hyde and hydrogen cyanide, cannot be dehydrated easily
to form acrylonitrile and water, since it tends to decom
pose into the original reagents at advanced temperatures.
To obviate this tendency of lactonitrile to decompose
into acetaldehyde and HCN, it has been proposed to acyl
ate the lactonitrile and then to pyrolyze the resultant
alpha-acyloxypropionic acid to obtain acrylonitrile and
the organic acid. Thus, lactonitrile is reacted with acetic
anhydride to form the alpha-acetoxypropionic acid, which
is then pyrolyzed to form acrylonitrile and acetic acid.
(Ritchie, Jones and Burns, U.S. Patent 2,183,357 (1939);
Miller and Groombridge, U.S. Patent 2,452,672 (1948).)
This process requires the use of an additional reagent
acetic anhydride-and the recovery and recycling of the 40
acetic acid formed.
More recently, a process has been developed for the
manufacture of acrylonitrile from acetaldehyde and hy
drogen cyanide which involves reacting these compounds
to form lactonitrile, mixing the lactonitrile with phos
phoric acid (nitrile-acid ratio about 2:1) and then spray
ing this reaction mixture under pressure into a reac
tion chamber, where it encounters pre-heated oxygen-free
combustion gases, at a temperature of about 600 C.
Dehydration occurs in about 0.1 to 0.6 second. Reac
tion products are cooled, condensed and separated.
The phosphoric acid is recovered in this process as
a solution of about 30% acid strength, which must then
be concentrated to 80%-85% acid strength before it can
be recycled to the process. About two-thirds of the
lactonitrile is thus dehydrated to acrylonitrile, the remain
der dissociating into acetaldehyde and HCN, which is
recycled in the process. Part of the lactonitrile reacts
with the phosphoric acid and the water present to form
lactic acid and primary ammonium phosphate
-NHHPO
About 7.5 kgs. of this ammonium phosphate is obtained
for every 100 kgs. of acrylonitrile formed. This salt
accumulates in the recycling phosphoric acid and must
be periodically separated from the system. This involves
a somewhat diminished yield of acrylonitrile, complicates
the phosphoric acid recovery, requires a concentration
and recycle system and involves the consumption of addi
tional phosphoric acid reagent. The overall yield of acry
lontrile by this process is about 90% of theory. This
process is described in U.S. Patent #2,790,822 (issued
April 30, 1957, to Wolfram, Steil and Agunte) and dis
3,151,150
2
cussed in Chemical Week (September 27, 1958), pp.
53-54, Chemical Engineering (June 1, 1957), pp. 42-44,
Chemical and Engineering News (December 1, 1958), pp.
49 and 98, and by Sennewald and Steil in Chemie-In
genieur-Technik, 30, #7, 440-446 (1958).
It is the purpose of my invention to provide a process
for the manufacture of acrylonitrile from acetaldehyde
and hydrogen cyanide which does not require reagents
other than acetaldeyhde and HCN and does not involve
O by-product recovery, which does not require concentra
tion and re-constitution of intermediates, and which gives
yields in excess of 90% of theory.
The basis of my invention is the finding that acryloni
trile may be obtained in excellent yield by the steps of:
(a) reacting lactonitrile (made from acetaldehyde and hy
drogen cyanide) with pre-formed acrylonitrile, in the
presence of a basic catalyst, to form alpha,beta'-dicyano
diethyl ether (alpha,beta'-oxydipropionitrile):
CH-CH-ON
CH3CHOEICN -- CII-CEICN - 9
CH2CH2CN
(b) pyrolyzing the alpha,beta'-dicyanodiethyl ether, at ad
vanced temperatures, to form (for each mole of said
ether) two moles of acrylonitrile and one mole of water
CH-CH-CN
o - 20EF2=CHCN -- HO
CHCHCN
One mole of the acrylonitrile thus obtained is recycled
to the first step of the process, for reaction with the lactoni.
trile to form the alpha,beta'-dicyanodiethyl ether. The
other mole of acrylonitrile is the salable end-product of
Said process.
Thus, the overall effect of the process is to form acry
lonitrile from acetaldehyde and hydrogen cyanide as sub
stantially the sole reagents.
Hansiey (in U.S. Patent #2,333,782 issued November
9, 1943) has shown that lactonitrile may be reacted with
acrylonitrile in the presence of an alkaline catalyst, to
form the alpha,beta'-dicyanodiethyl ether.
I have found that this alphabeta'-dicyanodiethyl ether
45
may be pyrolyzed over a very wide range of tempera
ture, in the absence of catalysts as well as in the pres
ence of dehydration catalysts, in the liquid phase and
in the vapor phase and at subatmospheric, atmospheric
and Super-atmospheric pressures, to give excellent overall
50
yields of acrylonitrile. It must be emphasized that, be
callse of the wide range and variety of operable reaction
conditions, I do not wish to be limited in the scope of
this invention to any specific range of temperatures, cata
lyst or reaction conditions.
55 The lactonitrile for the process of my invention may
be made by any of the well-known methods of the prior
art. Thus, for instance, liquid hydrogen cyanide is ad
justed to a pH between 6.0 and 8.0 with 20% aqueous
Soda. Solution. The stoichiometric amount of acetalde
60
hyde is then added with agitation at a temperature be
tWeen 10 C. and 25° C. to form actonitrile.
The Iactonitrile thus obtained may then be reacted
with acrylonitrile, in the presence of an alkaline catalyst
(e.g. alkali and alkaline earth metal hydroxides, alco
65
holates and cyanides, trialkyl amines, etc.), substantially
by the process of Hansley (U.S. Patent #2,333,782) to
form the desired alpha,beta'-dicyanodiethyl ether.
It is also entirely feasible to react acetaldehyde, hydro
gen cyanide and acrylonitrile, in the presence of an alka
70 line catalyst, in a single step, to form the alpha,beta'.
dicyanodiethyl ether.
The reaction of the acrylonitrile with the lactonitrile
 3,151,150
s 4.
(or with acetaldehyde and HCN if the reaction is effected
in a single step) is not quantitative. Thus, after the re
action of the acrylonitrile with the lactonitrile is effected,
the reaction mixture is fractionated to recover the alpha
beta-dicyanodiethyl ether and to recover and recycle the
various intermediates. Thus, the reaction product may
first be fractionated at atmospheric pressure. Acetalde
hyde and hydrogen cyanide (formed by the dissociation
of unreacted lactonitrile) distill over first (B. Pt. acetalde
hyde 21 C., hydrogen cyanide 26 C.). The unreacted
acrylonitrile (B. Pt. 78.5° C.) first distills over as an azeo
trope with the water present in the system. This azeo
trope boils at 71° C. and contains 88% of acrylonitrile
and 12% of water. The fractionation of the reaction mix
ture is then continued under reduced pressure, e.g. at
18-20 mm. Hg. The unreacted lactonitrile distills over at
90-100° C. at 18-20 mm. Hg, and the alphabeta'-dicy
anodiethyl ether may be recovered at 145° to 155 C. at
18-20 mm. Hg. However, in the practical application of
this process, it is only necessary to recover the acetalde
hyde, hydrogen cyanide, acrylonitrile and lactonitrile frac
tions. The residue in the still, consisting of the alpha
beta'-dicyanodiethyl ether, may be submitted directly to
pyrolysis for the formation of acrylonitrile, without prior
fractionation or purification. The recovered acetaldehyde,
hydrogen cyanide, acrylonitrile and lactonitrile fractions
are recycled to the process for the preparation of the
alpha,beta'-dicyanodiethyl ether. The conversion of the
actonitrile and the acrylonitrile to the alphabeta'-dicy
anodiethyl ether varies from 40% to 65% per cycle, but
the overall yield of the alpha,beta'-dicyanodiethyl ether,
based on the actual consumption of acetaldehyde, hydro
gen cyanide and acrylonitrile is 95% to 97% of theory.
The pyrolysis of the alpha,beta'-dicyanodiethyl ether
to form the acrylonitrile may be effected over a very wide
range of temperatures, in the absence of catalysts or in
the presence of dehydration catalysts, and at Subatmos
pheric, atmospheric or superatmospheric pressures.
In the absence of catalysts, the preferred (but by no
means the only effective) temperature range for the pyrol
ysis of the alphabeta'-dicyanodiethyl ether to acryloni
trile is 300° C. to 500 C.
The pyrolysis may be effected, in the absence of cata
lysts, by dropping the alphabeta'-dicyanodiethyl ether in
the liquid state on a heated surface, or by passing it in the
vapor phase over a heated surface, or through a heated
reaction zone or pyrolysis tube. The effluent gases are
cooled, condensed and fractionated to recover the end
products of the pyrolysis, including the acrylonitrile.
Alternately, a dehydration catalyst may be used. An
extremely wide range of such catalysts may be used in
the process of this invention.
Thus, the alphabeta'-dicyanodiethyl ether may be
dropped onto the surface of a heated catalyst (at 250 C.
to 750° C.) and thus pyrolyzed to acrylonitrile. The
catalyst may be solid or molten at the temperature of the
pyrolysis. Among suitable catalysts for this purpose are:
phosphoric acid, pyro-phosphoric and meta-phosphoric
acid, the alkali metal and alkaline earth metal oxides,
hydroxides, carbonates, and borates, the alkali metal and
alkaline earth metal salts of the fatty acids, the alkali
metal and ammonium salts of phosphoric acid, zinc salts,
aluminum salts, aluminum oxide, and many others.
- Phosphoric acid is an excellent catalyst for this purpose.
At 150 C., is becomes anhydrous; at about 200° C., it
reverts to pyrophosphoric acid and above 300° C. it is
largely present in the form of meta-phosphoric acid.
It must be emphasized that this phosphoric acid, in any
of its forms and dehydration products, acts as a true
catalyst. Unlike the phosphoric acid used in the process
of U.S. Patent #2,790,822 (above discussed), it is not
volatilized with the reaction mixture, it is not diluted by
the water of the reaction products, it does not have to be
concentrated and re-constituted and it does not hydrolyze
any of the starting materials or end-products to diammo
nium phosphate. The phosphoric acid remains in its
active catalyst form and may be used as such for pro
longed periods of time. The preferred (but by no means
solely effective) reaction temperature for the pyrolysis
employing phosphoric acid as a catalyst (or its dehydrated
forms-pyrophosphoric and metaphosphoric acid) is 300
C. to 400 C.
Alternately, the alphabeta'-dicyanodiethyl ether may
be passed in the vapor state through a catalyst bed, or a
heated reaction zone containing the catalyst, or through
0 heated tubes filled with the catalyst. Catalysts suitable
for this purpose are activated alumina, pumice, dia
tomaceous earth, fullers' earth, silica gel, Alundum, thoria,
dehydrating clays, etc. as well as supported catalysts such
as phosphoric acid or ammonium phosphates on any solid
carrier, such as activated alumina, pumice, kaolin, clay,
firebrick, silica gel, zinc chloride on any solid carrier
such as the above, etc.
Alternately, the vaporized alpha,beta'-dicyanodiethyl
ether may be passed, at advanced temperatures, through a
20 turbulent bed of any of the catalysts above enumerated,
in very finely divided form, by any of the technics now
used in fluid bed catalyzed reactions, and well known to
the art.
The preferred temperature ranges when employing such
25 solid catalysts, with the alpha,beta-dicyanodiethyl ether
in the vapor state, is from 250° C. to 450° C., but this is
by no means the solely operable or effective range. In
the presence of catalysts, the pyrolysis may be effected at
temperatures as high as 750° C. The use of a catalyst
30 is not essentiai, but may be preferred since it usually
gives a higher conversion to acrylonitrile per pass and
somewhat better overal yields, as does the use of higher
temperatures or temperatures within the indicated pre
ferred range.
The products of the pyrolysis of the alpha,beta'-dicy
anodiethyl ether, in each case, will consist of minor.
amounts of acetaldehyde (B. Pt. 21 C.), hydrogen cyanide
(B. Pt. 26° C.), water (B. Pt. 100° C.) and lactonitrile
(B. Pt. 90-100° C. at 18-20 mm. Hg), and substantial
40 amounts of the acrylonitrile (B. Pt. 78.5° C.) formed and
unreacted alphabeta'-dicyanodiethyl ether (B. Pt. 145
155 C. at 18-20 mm. Hg). It will be noted that these
products are the very same (although differing in relative
amounts) as those obtained in the fractionation of the
45
product obtained in the condensation of lactonitrile with
the acrylonitrile in the preparation of the alpha,beta'-di
cyanodiethyl ether (above described) which is the feed
for the pyrolysis reaction.
Thus, the end-product gases of the pyrolysis step, in
each case, may be cooled and condensed and then frac
50 tionated into its components. Alternately, the cooled,
condensed reaction products may be mixed with the re
action products from the condensation of lactonitrile
and acrylonitrile, and these combined products frac
tionated together. This will permit a considerable econ
ony in equipment and processing costs.
Thus, a fraction of acetaldehyde and hydrogen cy
anide may be recovered first, and recycled to the lacto
nitrile preparation. Then, the acrylonitrile may be re
60
covered (first as the azeotrope with water, and then as
pure acrylonitrile). Part of this acrylonitrile is recycled
to the preparation of the alpha,beta'-dicyanodiethyl ether
step, and the remainder represents the salable end-prod
uct of this process. Then, the unreacted lactonitrile is
recovered under reduced pressure, and recycled to the
65 process for reaction with the acrylonitrile to form the
alphabeta'-dicyanodiethyl ether. Finally, the still resi
due (which may be fractionated but must not necessarily
be so processed) is the alpha,beta'-dicyanodiethyl ether
which is the feedstock for the pyrolysis step.
70
The following examples are given to define and to il
lustrate this invention, but in no way to limit it to re
agents, proportions, catalysts, or reaction conditions de
scribed therein. Obvious modifications will occur to any
75 person skilled in the art.
 3,151,150
5 6
Example I
Lactonitrile is prepared by adding 20% aqueous caustic
soda solution to 271 grams of liquid hydrogen cyanide
(10 moles) to adjust its reaction to pH 7.0. A total of
443 gms, of acetaldehyde (10 moles) is now added slowly,
with good agitation, keeping the temperature of the re
action mixture between 10° C. and 25 C. In another
vessel, 531 grams of acrylonitrile (10 moles) and 5 grams
of potassium cyanide (as a catalyst) are heated under
gentle reflux, while the lactonitrile above formed is added
slowly over a period of an hour. The reaction mixture
is kept at 85°-90° C. for another hour, and is then cooled,
and adjusted to pH 7 by the addition of 20% sulfuric
acid. The product is then fractionated (as described in
the specification) first at atmospheric pressure, then at
18-20 mm. Hg pressure to recover acetaldehyde, hydro
gen cyanide, acrylonitrile, lactonitrile and the alpha,
beta- dicyanodiethyl ether. The conversion to alpha,
beta'-dicyanodiethyl ether varies from 40% to 65% per
cycle, but the overall yield, based on the actual consump
tion of acetaldehyde, hydrogen cyanide and acrylonitrile
is 95% to 97% of theory.
The alphabeta'-dicyanodiethyl ether is pyrolyzed by
adding it dropwise, at the rate of about 200 gms. per
hour, from a dropping funnel, into a 500 cc. flask, the
bottom of which is heated at 350° to 375 C. The gas
eous pyrolysis products are conducted off, cooled, con
densed and fractionated,
Alternately, the alphabeta'-dicyanodiethyl ether may
be pyrolyzed by vaporizing it under reduced pressure
(e.g. at 180°-200 C. under 20 mm. Hg. pressure), and
this is passed through a quartz tube (0.50' inside diam
eter, 15' long) at the rate of 75 gms, per hour, the tube
being maintained by electric heating elements at a tem
perature of 375 to 400 C. The gaseous pyrolysis
products are conducted off, cooled, condensed and frac
tionated.
The conversion of alphabeta-dicyanodiethyl ether to
acrylonitrile is from 32% to 70% per pass, and the over 40
all yield, based on the alpha,beta-dicyanodiethyl ether
actually consumed, is 93% to 96% of theory.
Example II
45
Fifty grams of phosphoric acid is placed in a reaction
flask and heated to 350-360° C. (which converts it
largely to meta-phosphoric acid). The alphabeta'-dicy
anodiethyl ether (prepared as described in Example I)
is added dropwise onto the surface of the acid from a 50 3. The process as defined in claim 1 wherein the pyrol
dropping funnel, at the rate of 50 gms. per hour. The re
action products of the pyrolysis are conducted off, cooled
condensed and fractionated.
The conversion to acrylonitrile is from 62% to 80%
per cycle, with overall yields of 94% to 95% based on 55
the alphabeta'-dicyanodiethyl ether consumed. Similar re
Sults are obtainable by the use of alkali metal and alkaline
earth metal oxides, hydroxides, carbonates and borates,
the alkali metal and alkaline earth metal salts of the fatty
acids, the alkali metal and ammonium salts of phosphoric
acid, Zinc salts, aluminum salts, aluminum oxide, and
many other dehydration catalysts.
Example III
Alpha,beta-dicyanodiethyl ether is vaporized under re
duced pressure (e.g. at 250-275 C. at 25-30 mm.) and
this is passed through a quartz tube (0.50' inside diam
eter, 15' long) half filled with activated alumina gran
ules as a catalyst, maintained at a temperature of 300
325 C., at the rate of 90 gms. per hour. The gaseous
pyrolysis products are conducted off, cooled, condensed
and fractionated.
O The conversion to acrylonitrile is 50%-55% per pass,
with an overall yield of 95% of theory, based on the
alphabeta'-dicyanodiethyl ether actually consumed.
Similar results are obtained by the use of catalysts such
as pumice, diatomaceous earth, fullers' earth, silica gel,
5
Alundum, thorium dioxide, dehydrating clays, supported
catalysts such as phosphoric acid or ammonium phos
phate on Solid carriers such as alumina, pumice, kaolin,
clay, firebrick, silica gel, zinc chloride, aluminum chlo
20 ride, etc.
Having described my invention, what I claim and de
sire to protect by Letters Patent is:
1. The cyclic process for the manufacture of acrylo
nitrile which comprises the steps of:
25 (a) reacting lactonitrile with acrylonitrile in the pres
ence of a basic catalyst to form alphabeta'-dicyano
diethyl ether,
(b) separating the alphabeta'-dicyanodiethyl ether
from unreacted lactonitrile and acrylonitrile,
30 (c) pyrolyzing the alpha,beta'-dicyanodiethyl ether to
form two moles of acrylonitrile and one mole of
Water for each mole of dicyanodiethyl ether con
Sumed, said pyrolysis being effected at a temperature
between 250° C. and 750° C. and at a pressure at
35 which the acrylonitrile formed is vaporized,
(d) recovering acrylonitrile and unreacted dicyano
diethyl ether from the pyrolysis products of step c,
(e) recycling to step c the unreacted alpha,beta'-dicy
anodiethyl ether recovered from step d,
(f) recycling to step a the unreacted acrylonitrile
and lactonitrile from step b together with a portion
of acrylonitrile from step d equal to the amount of
acrylonitrile which had been consumed in step a
and
(g) recovering as product from step d an amount of
acrylonitrile stoichiometrically equivalent to at least
90% of the lactonitrile consumed in the process.
2. The process as defined in claim 1 wherein the py
rolysis is effected at a temperature of 300° C. to 500°C.
ysis is effected in the presence of a dehydration catalyst.
4. The process as defined in claim 3 wherein the pyrol
ysis is effected at a temperature of 250° C. to 450° C.
References Cited in the file of this patent
UNITED STATES PATENTS
2,333,782 Hansley --------------- Nov. 9, 1943
2,562,583 Schulz et al. ------------ July 31, 1951
2,832,798 Rapoport ------------- Apr. 29, 1958
60 OTHER REFERENCES
Institute of Synthetic Organic Chemical Research C.A.,
44 (1950), page 3515 (B).